Metal additives composition and its effect on

lubricant characteristic
Cite as: AIP Conference Proceedings 1774, 040001 (2016); https://doi.org/10.1063/1.4965083
Published Online: 19 October 2016

Azmi. Roslan, Ahmmed. S. Ibrahem, and Abdul Hadi

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© 2016 Author(s).
 Metal Additives Composition and Its Effect on Lubricant
Characteristic

Azmi. Roslan1, a), Ahmmed.S.Ibrahem2, b) and Abdul Hadi3, c)

1
Faculty of Chemical Engineering, Universiti Teknologi MARA, Pasir Gudang, Masai, Johor, Malaysia.
2
Chemical Engineering Department, Dhofar University, Salalah, Oman.
3
Faculty of Chemical Engineering, Universiti Teknologi MARA, Shah Alam, Selangor, Malaysia.
a)
Corresponding author: azmiroslan@salam.uitm.edu.my
b)
aibrehem@du.edu.om
c)
hadi9598@salam.uitm.edu.my

Abstract. This study present and discuss the effect of metal additives compositions in SAE10W-30 engine oil by
evaluating its thermal mass and viscosity behaviour. Five types of engine oils from commercially available lubricant and
represented the highest quality of SAE 10W-30 oils from each manufacturer were used in experimental section, which
are Oil 1, Oil 2, Oil 3, Oil 4, and Oil 5. The oils were fractionated using chromatographic method and the metal additives
in the engine oils assessed in the form of its ions present. Viscosity behaviour obtained using rotational viscometer under
constant shear rate of 600 s-1 and temperature from 40 to 100 0C. The area under the curve method using 1/3 Simpsons
rule was employed by means of evaluating engine oil performance. Heat capacity for each samples were determined
using bomb calorimeter in adiabatic mode of operation. The study led to following conclusions; Oil 4 had shown
significantly best performance of engine oils amongst the other. Oil 5 exhibits the best performance for viscosity because
time required to achieve 100oC is longer than the other with 40.6 minutes.

Keywords: Metal additives, lubricant, Viscosity, and heat capacity

INTRODUCTION

Lubricant is a substance capable of reducing friction, heat, and wear by forming a protective layer between two
metal surfaces in contact. Besides that, lubricant also bring along with six different functionality; provision of stable
oil film between sliding surfaces, provision of reliable engine operation in a wide temperature range, rust or
corrosion protection of engine parts, cleaning the engine parts from sludge, sealing piston ring-cylinder gap and
cooling the engine parts. Therefore, lubricant formulation is tailor made based on its viscosity as to fulfil its primary
function to reduce friction [16] in diverse area of application such as industrial, hydraulic system, machining and
automotive. Viscosity is temperature dependent [1 and 2]. When the lubricant absorbed heat energy from its
surrounding, the molecules vibrate more rapidly at random, and in doing so establish a space around them which is
proportional to their kinetic energy [4]. If the local engine temperature is substantially higher, the space created will
be far that is equivalent to kinetic energy of particle absorbed, thus speed up the thinning effect of lubricant. The
viscosity must be high enough to maintain a lubricating film, but low enough that the oil can flow around the engine
parts under all conditions [5 and 6]. Some researchers reported that with lower viscosity at high temperature
operating engine condition, the lubricant could provide reduction in friction and may lead to the high fuel
consumption efficiency [2 and 3].

International Conference on Advanced Science, Engineering and Technology (ICASET) 2015

AIP Conf. Proc. 1774, 040001-1–040001-7; doi: 10.1063/1.4965083
Published by AIP Publishing. 978-0-7354-1432-7/$30.00

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 Automotive car operates internal combustion engine to convert chemical energy into mechanical energy as to
move car forwards. Combustion process normally releasing heat significantly higher than 100˚C and may lead to the
engine overheating. Lubrication system is design to provide a sufficient amount of lubricating oil to all engine parts
at all engine operating condition. As a consequences, heat energy possesses by the engine is indirectly absorbed by
the lubricant. Hence, lubricant functionality as friction reducer may be disrupted as lubricant viscosity is affected.
There are nine different types of additives blended in lubricant, in which, carry out different functionality. On
average, typical engine oil may constitute 15 to 25 additives percent by weight and 75 to 85 percent by weight of
base oil [7]. A metal additive is one of them and commonly known as anti-wear additives, constitutes about 0.04 to
0.09 wt% [16] in typical lubricant formulation. It is consumed in providing a protective layer in between metal-to-
metal contact by adding film-forming compounds that protect the surfaces either by physical adsorption or chemical
reaction [7 and 8]. This coating protects the part surface from a direct contact with other part, decreasing wear and
scoring [8 and 9]. The main elements, which are responsible for the extreme pressure and anti-wear action, are
sulphur and phosphorus [10]. Metal dialkyl dithiophosphate compounds are commonly used additive in lubricating
oils due to its multifunctional performance as anti-wear, extreme pressure, friction modifying, antioxidant and
corrosion inhibiting additives [10 and 11]. Besides that, dialkyl dithiophosphates of different metals, such as
molybdenum [12 and 13], cadmium, copper [14], titanium [15], gadolinium, iron, tin [11], antimony [11], and other
metals, also have been introduced in lubricants, although zinc dialkyl dithiophosphates (ZDDP) are the most widely
used [10].
However, marketers did not disclose the types of additives and their concentrations to the public due to their
importance and highly-details. Moreover, the technology also protected via formal patents or other intellectual
property protection mechanism to prevent rivals from copying. This research is realized on the difficulty in
specifying the metal additives used in order to study the effect that they can offers to lubricant properties. In this
work, system analysis is performed for determination of metal additives compositions in five different brands of
SAE10W-30 engine oil by assessing metal ions concentrations using inductively coupled plasma optical emission
spectrometer (ICP-OES). The information was then compared with the heat capacity, viscosity data and Cloud and
Pour Point. It is expected that, system analysis will provides information on the effect of metal additives
combination in engine oil.

METHODOLOGY

Sample Preparation

Five commercially available mineral engine oil brands represented the highest quality of SAE 10W-30 oils by
different manufacturer were used for experimental purposes. They are denoted as Oil 1, Oil 2, Oil 3, Oil 4, and Oil
5. Dilution with kerosene 1/10 weight per volume basis was conducted as to run experiment using Inductively
Coupled Plasma Optical Emission Spectrometry (ICP-OES) requires samples with low viscosities. All samples were
subsequently transferred to an incubator shaker with operating condition at 25˚C and 150 revolutions per minutes
(rpm) for 30 minutes to achieve a uniform mixture of kerosene and oil.

Engine Oils Cloud and Pour Point Determination

Cold flow properties for all samples were evaluated by STANHOPE-SETA Cloud and Pour Point Cryostat
according to ASTM D2500-IP 219 and ASTM D97-IP15 consists of three 2 liter compartments independently
controlled between ambient and -34 ˚C with a stability of ± 1.5 ˚C. The reagent (cooling medium) used in this
equipment is methanol. The bath temperature was set to the lowest temperature as possible at -34 ˚C. The test was
performed by observing formation of paraffin wax at the bottom of the jar tester. For every subsequent 3 ˚C, jar
tester is removed and tilted horizontally for 5 seconds to check surface movement. If it does not flow, 3 ˚C is added
to the corresponding temperature and that is pour point temperature.
.

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 Metals Additive Identification

An iCAP 6000 series Inductively Coupled Plasma Optical Emission Spectrometer (ICP-OES), featuring a
27.12MHz RF generator. Analytical signals are measured using the RACID86 Charge Injection Device (CID), the
detector of choice for ICP emission spectroscopy. The analytical wavelength range is a no compromise 166.25-
847.0 nm allowing full access to all elements that can be determined by ICP. For optimum operation, the nebulizer
pressure was set at 160 kPa which compares to 170 kPa while running aqueous solution. The nebulizer pressure
varies depending on the solvent type and to minimize any potential carbon build up on the rims of two inner tubes
and injector tip of the torch, the auxiliary gas flow was set to 1.0 L/min.

Heat Capacity of Engine Oils

Heat capacity of engine oils was evaluated by IKA Calorimeter system C5000 control (Bomb Calorimeter). The
operating condition for the system was set to adiabatic. All 4 samples were measured with consistent amount and
weight of 0.9977 g in crucible pan and fit in into decomposition vessel. In this experimental works, cotton thread
was used as an ignition wire to the system. Repeatability test was run and the average heat capacity is determined.

Viscosity Behaviours

Approximately 180 ml of samples were prepared for this experiment. Viscosity behaviours was performed using
Grace Instrument M3600 Viscometer, a true Couette, coaxial cylinder, rotational viscometer with rotor radius of
1.7245 cm and bob effective length is 3.8 cm. This is an automated rotational viscometer. All tests were run for a
constant shear rate of 600 s-1 and temperature at 40˚C to 100˚C with temperature correction of 5˚F. The shear stress
was recorded throughout each test by means of shear rate to measure the absolute viscosity of samples at different
temperature. Time taken for samples to reach 100˚C also was recorded. The performance of viscosity-temperature
relationships were characterized using 1/3 Simpson’s Rule by determining area under the curve.

RESULTS AND DISCUSSION

Engine Oils Density and Cloud and Pour Point Determination

Table 1 shows the result obtained from the engine oil density and cold flow properties analysis. As can be seen
in the table, Oil 4 had shown significantly higher density with respect to the others followed by Oil 1, Oil 2, Oil 3,
and Oil 5. Therefore, Oil 4 is much heavier than the others. A possible explanation for this might be that atomic
structure of the elements, molecules and compounds that makes it up. Different elements, molecules and compounds
exhibit different molecular weight. Based on these results, the following ranking was obtained: Oil 4 > Oil 5 > Oil
2> Oil 1 > Oil 3.
The results, as shown in Table 1 indicate that Oil 3 had the lowest temperature than Oil 1, Oil 2, Oil 4, and Oil 5.
The interesting about this data is that amongst all engine oil, Oil 3 has probably contain a least amount of wax
paraffin’s compared to others. Since, engine oil pour point ability is only affected by the amount of wax paraffin.
Further analysis showed that the pour point temperature gaps of all oils were not so vary. Besides that, the cloud
point also observed where at this point of temperature, the paraffin wax will start to form a crystallization structure
and separate from the oil. This formation was observed when samples shown cloudy appearance, and thus
precipitated at the bottom of the graduated beaker. Generally, it was found at 0˚C for all samples. The observed
increase in precipitation could be attributed to the transition state of wax paraffin’s of oil from liquid to solid phase.
Wax paraffin’s is much denser in solid than in liquid phase, and this would make it is no longer soluble in the oils,

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thus precipitated at the bottom of the graduated beaker. This will continuously occur until all wax paraffin’s in the
oil has completely formed a solid phase; this temperature is called Pour Point.
. TABLE 1. The Density at 25˚C, Specific Gravity at 25˚C, Pour Point and Heat Capacity of Oil 1, Oil 2, Oil 3, Oil
4 and Oil 5
Density
Engine Specific Heat
Mass, at Pour
oil gravity Capacity,
kg 25˚C, Point, ˚C
brand at 25˚C J/K
kgm-3
Oil 1 0.03168 792.00 0.79 -33.3722 44374.134
Oil 2 0.03195 798.75 0.80 -33.6722 45034.092
Oil 3 0.03122 780.50 0.78 -35.1722 44562.6009
Oil 4 0.03436 859.00 0.86 -33.5000 44424.5879
Oil 5 0.03342 835.50 0.84 -34.0000 44822.8347

Metals Additive Identification

In Table 2, the elements with their concentration was assessed and tabulated. The metal additive usually utilized
in engine oils act as an anti-wear or friction reduction media. They are forming protective film by physical or
chemical absorption to the surface of the metal in contact. Thus lead to the sliding friction reduction. Each of the
elements has their own specific heat capacity, and their presence may lead to the improvement on the capability of
engine oil in absorbing heat from its surrounding. Therefore, lube base stock formulated with those elements will be
improved in its heat capacity of the mixture. But, some of the elements present in the engine oil may be unnecessary
due to its negative effect to the heat capacity and viscosity of the engine oil. These elements may be originated from
external source. Understanding of elements direction to engine oil quality is necessary before optimized blend of
metal additives could be achieved.

TABLE 2. Element Concentration of Engine Oils in ppm Using ICP-OES

Concentration of elements (in ppm)
Element
Oil 1 Oil 2 Oil 3 Oil 4 Oil 5
Fe 0.006249 0.044767 0.000187 0.015998 0.022654
Cr - - - 0.000865 2.09E-05
Ni 0.098505 - - 0.086207 0.157488
Zn 48.2245 63.0884 65.2278 52.1113 46.0837
Cu I 0.035079 0.415973 0.104755 0.041073 0.02845
Cu II 0.026582 0.289386 0.077015 0.039839 0.027068
Mg 6.37502 - - 5.74604 3.8203
Pb - - 0.002112 0.002657 -
Mn 0.001916 0.003116 0.001403 0.002983 0.003228
Mo - - - 0.833855 1.25691
Ti 0.258156 0.233275 0.249176 0.268929 0.270225
V - 0.02312 0.058485 0.08057 0.074827
Li 0.281614 0.016414 - 0.056044 -
Co - - - 3.64E-06 -
Cd 0.240688 0.608496 0.505425 0.318925 0.19555
As 0.282672 0.314322 0.28634 0.275895 0.273279
.

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 Heat Capacity of Engine Oils

Table 1 indicates the heat capacity of all five engine oil brands. Oil 2 had significantly shown the highest value
in heat capacity followed by Oil 3, Oil 4, Oil 5 and Oil 1. Heat capacity is an indicator to the effectiveness of
substances to be as cooling agent in the engine (in the case of engine oil). Nowadays, most, not all, locomotive
automotive vehicles ability is generated by internal combustion engine. The combustion process occurs may
increase local temperature of an engine and thus affecting the most important engine oil property which is viscosity.
Viscosity of engine oil is easily to be fluctuated by temperature. The samples exhibiting higher value of heat
capacity can absorb higher heat from surrounding. Metals composition in the engine oils also helps in absorbing heat
since they are also have their own specific heat capacity. Therefore, metals composition in engine oils not only
giving anti-wear or extreme pressure additives but also exhibiting as a heat absorber. Other than that, by increasing
the amount of fluid thermal mass, it will increase sustainability of engine oil viscosity over wide temperature range
thus maximize of its usage.

Viscosity Behaviours

Figure 1 shown the comparison of engine oils viscosity at temperature of 32˚C to 100 ˚C, at 40˚C, Oil 3 showed
lower viscosity than Oil 5, but at 100 ˚C, its viscosity was similar to each other (10.1668 cP). Observation on the
time taken for a sample to reach temperature of 100 ˚C had turn out to be an important parameter consideration since
good lubricant must possesses sustainable viscosity to the temperature increment. The sample with longest time
taken is good because the oil will slowly reduce its viscosity but at the same time sustaining their viscosity through
temperature increments. In this experiment, Oil 5 has the longest time taken, 40.6 min. followed by Oil 2 (36.67
min), Oil 3 (36.67 min), Oil 1 (36.1 min) and Oil 4 (35.98 min). Estimation of area under the curve for each of the
samples graph shows that Oil 5 had the highest area under the curve with 4061.45952 followed by Oil 3
(3765.5496), Oil 2 (3651.57168), Oil 4 (3638.61744) and Oil 1 (3460.83144). This shows that, Oil 5 exhibits
sustainability in viscosity when subjected to temperature change.
oil formulation.

FIGURE 1. Engine Oil Viscosity Comparison for all Engine Oil at Temperature of 32 to 100 0C

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 CONCLUSIONS

As a conclusion, Oil 5 had shown significantly best performance of engine oils amongst the other four. The pour
point limit is the limit where the engine oils can flow around the engine to give protection to engine parts. The lower
the pour point is better. Generally, all engine oils have a good pour point. Since the gap between them is not far. Oil
5 exhibits the best performance for viscosity because time required to achieve 100oC is higher than the other with
40.6 min. Oil 5 does not possesses a high heat capacity because, as information to ICP-OES analysis, it has shown
that, Oil 5 is lack on cobalt and lithium ions in its formulation. Nevertheless, the percentage different was not too
high, and it is about 0.47% compared to Oil 4. Data on the time taken for Oil 4 shown that, it takes about on average
of 1.53 minutes faster to increase temperature of the oil to 100˚C compared to Oil 1, Oil 2, Oil 3, and Oil 5. By
comparing result from ICP-OES, it shown that cobalt element brings a negative effects to the engine oil viscosity.
Oil 2 possesses high heat capacity compared with other engine oil. Comparison between Oil 2, Oil 1 and Oil 3 had
shown that, elements such as chromium, nickel, magnesium, lead, molybdenum are not necessary to be blended in
engine oil formulation.

ACKNOWLEDGMENTS

This research work was supported by the Faculty of Chemical Engineering, Universiti Teknologi MARA
(UiTM), Johor Branch, Pasir Gudang Campus, Faculty of Chemical Engineering, Universiti Teknologi MARA
(UiTM), Shah Alam, Selangor and the Research Acculturation Grant Scheme (RAGS) from the Ministry of Higher
Education Malaysia (Grant No. RAGS/1/2014/TK05/UITM//3).

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